Monoaroyldiamines of the benzene series



Patented Sept. 20, 1932 i f l nsrATEs PATENT- oFFicE nncnn nnuntn, EUGEH enrnrnnnnnognnn WILHEL'M NEELMEIER, or r nvnnx'osnn- ONATHE-REIN'E. GERMANY, ASS'IGITOBS TD. GENERAL, AKILINE. M03435; INC-,7. OF a new Yonn, n. Y.,e conronnrron or DELAWARE nononnortmnmnns: on THE Benzene SERIES hie Brewing; Anplicationfiled Dec mber 5, 1Q3Q,,S,eria1 No. 500,417, andin Germany December 23, 1929.

The present invention relates to aprocessof preparing; nionoaroyl-diemines of thebenzene series and to the new products obtainable thereby, moreparticularly it; relates to corn pounds of the general formula: V

ing solubility of the aroylated nitranilines and of the reduction products in water and in the customary organic solvents, such as alcohol, benezene and the like the process presents technical difficulties in many cases.

In accordance with the present invention monoaroylphenylene*diamines oi the above general formula are produced in a smooth reaction aroylating or alkaroylating in the usual manner the amino group of a, l-amin 8- or l-arylsulfa1nido benzene which may be represented by the general formulae- I one y meaning the group -NHSO aryl,i the other 3/ meaning hydrogen, halogen, alkyl or oxalkyl and wherein the benzene nucleus maybe '1 urther substitutedhy' halogen, alkyl or oxallryl, by'treating the some with an aromatic-aliphatic carboxylic acid' halide in aqueous solution in thejiresence of an acid binding agent.

The starting an ino-arylsulfamido benzenes are obtainable according to known'methods by reacting; upon a l-ni-tro-l-or 2-a'mi no benzone which may be otherwise substitutedby l halogen, v I sulfonic acid halide, such asbenzene sulfonlc acid chloride or para-toluene-sulfonie acid chloride in aqueous solution in the presence of an acid binding agent, and reducing the nitro group to form the. amino group,for example, by means of iron and hydrochloric or aceticacid. v

From the ar yl sulfonic compounds of the formula the aryl sulfonic'acid group is; split oil introducing the compound intov concentrated alkyl or oXalkyl with an aromati sulfurie'acid of room temperature. and ullow-v j ing the sulfuric acid to act upon theicome pound for several hours, whereby the aroylamino group is not attacked. V V

The whole processmay he represented by the following scheme: NE: NH-SOrary1 NH-SO;;-ery1NH-SOg-a1{yl ron; v 2 'NH2 0 NH CO- X' nH oo x The process described also; renders possible in many cases the manufacture of bases, which r the formula in consequence of the difficulty of obtaining the nitroamino compounds could only be produced by other methods in a tedious or cumbersome manner. Thus the monoaroylphenylene-diamines heretofore unknown of on OR NH, from ar 1son n1 aryl-OO-NH as methyl orethyl I i. ,7 R I V A were only to'be obtained from the nitroamine of the formula:

' tong"; I

being only accessible with difficulty. v-,'- lhe new compounds thus obtainable are; generally white,to yellowish colored crystalline. substances andare valuable interniediate products dyestufls.[;:;- m v v:The following examples will illustratethe' invention, without restricting it thereto:

in the ,manufac'ture of azo w mpl l (a) 322 kgs. of the 5-nitro-4-methyl-2-l phenyl-sulfamido-l-methoxybenzene, melting at 207-208 (3., obtainable in accordance with Brit. specification No. 6741/1904, are

- reduced by means of iron and hydrochloric acid. Themixture is then rendered alkaline with caustic soda lye, and the amino compound, present in the solution, is pressed out 7 from the iron sludge.

160 kgs. of benzoylchloride are then added gradually to the filtrate' at 3040"C. with thorough stirring" whereupon the" benzoyl compound formed precipitates. washed with water anddried. The melting point is 168171 C. I H

396 kgs. of the 5 benzoylamino at-methyl- Q-phenyl-sulfamido-1-methoxybenzene thus produced are introduced at 2030 G. into 3.5 timesthe. quantity of,669 B..sulfuric acid. Solution occurs. On the following day the solution is poured on to ice.

separates out as the sulfate. It is filtered with suction and washed with sodium chloride so, lution until neutral. The sulfate is dissolved.

in hotwater, pressed through a filter and the 1 free base is precipitated with sodium carbonate.

It consists of whitesmall needles, melting at 185 C. r r

When in the above exampleinstead of 5- nitro-4 -methyl-2-phenylsulfamido-1-methoxybenzene the 5 nitro-4-methyl-2-phenylsul 2-amino-phenylbutylether (melting methyl -2- methyl-2-tamino-l-methoxybenzene.

This is filtered by suction,

v The 5-benzoylamino-l-methyl-EZ- amino 1 methoxybenzene,

famido-l-ethoxybenzene (melting at 175 C.) is reduced in the customary manner by means of iron and hydrochloric acid and the solution after being rendered alkaline with caustic soda and filtering from iron is benzoylated in the manner above described, the 5- benzoylamino 4- methyl -2-phenylsulfamidol-ethoxybenzene, melting at 148 C. is ob tained. 7

'When the latter substance is introduced into four parts of 66 B. sulfuric acid, al-

lowed tostand for 2 1 hours and then poured 1 on to ice, tl 1e sulfate of the fi-benzoylamino-t- -methyl-2-amino-l-ethoxybenzene separates out. By dissolving in hot water, filtering and precipitating with sodium carbonate, the

' free base is obtained,melting at 158 C.

The sulfate of the benzoylaminol-methylpoint of the base 120? G.) is obtained. by reduction, subsequent benzoylation and splitting up with'conc'entrated sulfuric acid of the 5 nitro- 4+ methyl 2 phenylsulfamido-phenylbutyl ether of the melting point 134 C.

' b) The 5 (2.4-dichlorobenzoylamin'o) 7 'OOHs e t v a. a

melting at 16090. is obtained."

' Onusing instead of'benzoylchloride the 4- methxoybenzoylchloride and decomposing the condensation product with sulfuric acid, the sulfate of 5- (4-methoxybenzoylamino) 4-111e'thyl-2 amino l-methoxybenzene,melting at 212 (1, is obtained.

The phenylacetic acid chloride yields on condensing with 5-amino l-methyl-2-phenylsulfamido-l-methoxybenzene the 5-phenylacetylamino 4- methyl-2 -phenylsu1famido-1- metho'xybenzene of the melting point 183 V on heating this mixture for. a short time with 4 partsof concentrated sulfuric acid, there is obtained the sulfate of the 5i-phenylacetylamino 4- methyl -2- .amino-l-methoxybenzenenfThe free base, has. the melting p oint l'589 C;

2-chloro-phenoXy acetic 7 acid chloride amin'o-tmethyl-SZ- amino-l-methoxybenzene results. l

Example f 356.5 kgs. of the 5-nitro-4c-chloro2-tolylsulfamido-l-methoxybenzene, melting at 170 (1., produced in accordancejwith Brit. Spec. No. 6741/1904, are reduced by means of iron and formicacid and after rendering alkaline with caustic'sodaand separating from the iron, the amino compound is treated with 160 kgs. of benzoyl chloride at 25-30 C..:with thorough stirring. The condensation product separates out "after some time. It is filtered by suction, washed and dried. The melting point is175 C.

100 kgs. of 5-benzoylamino--chloro-2 tolylsulfamido-l-methoxybenzene are introduced at room temperatureintoOO kgs. of 98% sulfuric acid, allowedtostand for 241 hours, after which the solution is poured into ice water. The sulfate of the 5-benzoylamino-l-chloro-Qemino 1 -niethoxybenzene separates out and is filtered with suction and washed with salt solution. 7 It is dissolved in hot water and after filtration the base of the formula:

V 7 NH:

is precipitated with ammonia. small snow white needles, melting at 17 It forms E wample' 3 306 kgs. of 2-methyl-4-nitro-l-tolylsulfamidoben'zene are reduced in the customary manner by means of iron and hydrochloric acid. When theoreduction is complete, the mixture is rendered alkaline with caustic soda and filtered from the iron sludge. 141

kgs. of benzoylchloride are introduced slow-' ly into the filtrate at EEO-40 C. while stirring.

and is filtered by suction and dried. The

. melting point is 195 C.

i 100 kgs'of the latter compound areintro- The benzoyl compound precipitates duced into kgs. of 98% sulfuric acid and allowed to standfor 1-2 days,'when the solu tion is-poured onto ice.

The sulfate of the 2 methyl 1 5be nzoylphenylenediamine separates out. It is dissolvedfinhot waterand after the addition of sodium carbonate the free baseof'the formula'z" f 7 v 7 CH3 I i f o is obtained. It forms whiteneedles melting 1549 t I Ewamplc' il.

I 166 kgs of G-nitr -iemino-L3Qdiniethyl-' benzene are dissolvedat 0., in an equal quantity of pyridine and 17 7 kgsQof' benzene sulfochloride are added between 60 and C. While stirring. After furtherstirring for one half toone hour 300 kgs. of water are added and the phenyls'ulfamido-nitro-Xylene, which crystallizes out, is filtered by suc-' tion, washed with a little'water and dried. The melting point is 148? C. r e r 306 kgs. of the above product are reduced in the customary manner iniQIQOO litersrof waterby means of 300 kgshofironand 20 kgs. of hydrochloric acid;, After rendering alkaline with caustic soda lye and separatingfrom the iron by pressing, 141'kgs'.-of-benzoyl chloride are stirred into thediquor.

The benzoyl compound, whichiseparates, is

of the formula separates as the sulfate. This is dissolved in hot water, filtered and the base-isprecipi, tated with sodium carbonate. It forms white needles, melting at 176 C.

f'EmampZe 5- whereupon the 6-benzoylamino-4- 168 of l-nitrO-Z-anisidine are dissolyed" in 336 kgs. pyridine and 191 kgs." para toluene-sulfochloride are added at 60-430? C, After about one half hour the solution is diluted with 20O 'liters of water, and the toluenesulfo compound which crystallizes out is filtered-by suction and washed untilneuf tral. The meltin'gpoint is 19 1 O.

7m 1 eand se aratin from h iron sludge by y P g day. The solution is poured on to ice and the product which" separates is filtered by b suction. The solution is re-dissolved in hot water, filtered and from the filtratejthere.

' is precipitated with sodium carbonate the V c It is filtered by introduced into washed with a solution of of the formula .4 benzoylamino g 2 amino l mejthoxyb enzene of the melting aint i159? o; i

(a) 339 kgs. of 5-nitro-2 phenylsulfamido i 1 4 hydroquinone-dimethylether of the melt ing point 198 (3., obtained in accordance with Brit. Spec. N 0. 6741/1904, are reduced in the customary manner 'with iron and acetic acid. After rendering alkaline with, caustic soda suction, 150 kgs. of benzoylchloride are added to the liquor while' thoroughly, stirring, whereby the l benzoyl .compoundf separates. suction. while still alkaline and dried. Th e melting point is 175 C.

100 kgs. of 5-benzoylaminoe2-phenylsulfamido-1.4-hydroquin0ne-dimethylether are 400 kgs. of 66 B. sulfuric acid and stirred for about 24 hours at 2030 C. Thesolution is-then poured on to ice; the sulfate of the 5-benzoylamino- 2- amino 1.4 hydroquinonedimethylether which separates is filtered by suction and common salt.

After re-dissolving in hot water the base is filtered and precipitated with sodium carbonate. lt forms-white needles, melting at (b) By treating the smart-2 151411715111- famido-l;4-hydroquinone-diethylether in the same manner as described under a), of this ex ample, there is obtained as end 7 productthe 5 benzoylariiino-Q-amino-1.4 hydro-quin0ne i diethylether of the melting point 101}? O. f

B. and allowed to. stand for one.

(0) When the 5-nitro-2 amino-4 methoxy- 1- ethoxybenzene (prepared in accordance withfGerman PatNo. 141,975) is condensed with benzenesulfochloride in pyridine, and

thebenzenesulfocompound thus obtained is reducedin the; same manner as described under a) ofthisexample, the 5-benzoylam:

ino-2-amino:4-methoxy-l-ethoxybenzene of the formula: I i

. i i NH2 00m 1 f '1 of the melting point 121 C. results after enzoylating and'splitting 011' the benzene sulfo residue.

i I l V I.1--Y

*1. The-Zprocess whichcomprises acy-l'ating a l-amino-benzene which is substituted in one 1 of the positions '3 and '4" byjthergroup -;'NHSO aryl.and which may be further a substituted b subs'tituents of the groups con.

sisting of al 1, oxalkyl and halogen with an acid halide of an organic acid of the group I consisting ofcarboxylic acids of the aromatic and aromatic-aliphatic seriesand' reacting upon the aminoacyl compound formed with concentrated sulfuric acid ture for several hours. V 1 2.'The process which comprises acylating a l-am'in'o-ben'zene'which is substituted in one of the positions "3 "and 4 by the groups NH SO O H and which may be furat room temperather' substitutedby substituents of the groups consistingof alkyl, oxalkyland hal ogen with an acid chloride of an-organic acid of the group-consisting of carboxylic acids of thearomatic and aromatic-aliphaticseries .and reacting upon the acylamino compound formed with concentrated sulfuric acid at room temperature for several hours.

3. The process which comprises acylating a l-amino-benzene which is substituted in one of the positions 3 and 4-by the group substituted V p with an acid halideof an organic acidofthe group consisting ofcarboxylic acids of the aromatic and aromatic-aliphatic series and reacting upon the acylamino compound formed with concentrated sulfuriciacid at room temperature for several hours.

4. The process which comprises 'acylating a l-amino-benzene which is substituted in one of the NH SO aryl and whichgmay be fur-x thersubstituted by an alkyl and {oxalkyl group with an acid chloride of an organic, acid'loflthe group consisting of carb'oxylic acids of the aromatic and positions 3 and 4 by the grofups series. and reacting upon the, acylamino 1Com aromatic-aliphatic arc O aryl and which may be further 7 by an alkyl and oxalkyl group lap pound formed with concentrated sulfuric acid at room temperature for several hours.

5. The process which comprises benzoylatiug a l-amino-benzene which is substituted in one of the positions 3 and 4 by the group NHSO -O H and which may be further substituted by substituents of the group consisting of alkyl, oxalkyl and halogen and reacting upon the benzoylamino compound formed with concentrated sulfuric acid at room temperature for several hours.

6. The process which comprises benzoylating a l-amino-benzene which is substituted in one of the positions 3 and 4 by the group NH-SO C H and which is further substituted by an alkyl and oxalkyl group and reacting upon the benzoylamino compound formed with concentrated sulfuric acid at room temperature for several hours.

7. The process which comprises benzoylating 5-amino-A-methyl-2-phenylsulfarhido-1- methoxybenzene with 2.4edichlorobenzoylchloride and treating the QAfdichlorobenzoylamino compound formed with concentrated sulfuric acid at room temperature for several hours.

8. As new products monoaroylphenylenediamines of the general formula wherein R and R stand for alkyl, being generally white to yellowish colored crystalline substances which are valuable intermediate wherein R and R stand for alkyl groups from 1 to 2 carbon atoms, being generally white to yellowish colored crystalline substances which are valuable intermediate products in the manufacture of azo dyestulfs.

10. As a new product the compound of the formula:

(MOO C-NH being a yellowish crystalline substance of In testimony whereof, we afiix our signatures.

EUGEN RIMELE. EUGEN GLIETENBERG. WILHELM NEELMEIER. 

